CN108176241B - Composite nanofiltration membrane containing aquaporin and preparation method thereof - Google Patents
Composite nanofiltration membrane containing aquaporin and preparation method thereof Download PDFInfo
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- CN108176241B CN108176241B CN201711329227.0A CN201711329227A CN108176241B CN 108176241 B CN108176241 B CN 108176241B CN 201711329227 A CN201711329227 A CN 201711329227A CN 108176241 B CN108176241 B CN 108176241B
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Abstract
The invention provides a composite nanofiltration membrane containing aquaporin and a preparation method thereof. The preparation method comprises the following steps: step S1, arranging the aquaporin vesicles and a polyamine aqueous phase monomer solution on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the polyamine aqueous phase monomer solution comprises polyamine, a surfactant, an acid acceptor and water; step S2, carrying out secondary surface treatment on the surface treatment porous supporting layer by using a polybasic acyl chloride oil phase monomer solution to obtain a composite nanofiltration preparation membrane; and step S3, drying the composite nanofiltration preparation membrane to obtain a composite nanofiltration membrane, wherein the composite nanofiltration membrane comprises a porous supporting layer and a polyamide layer formed by polymerization, and aquaporin vesicles are dispersed in the polyamide layer, so that aquaporin activity can be protected, the strength of the composite nanofiltration membrane is ensured, the water flux of the membrane is obviously improved, and the anti-pollution capacity of the membrane is enhanced.
Description
Technical Field
The invention relates to the field of composite membrane materials, and particularly relates to a composite nanofiltration membrane containing aquaporin and a preparation method thereof.
Background
The nanofiltration membrane is a pressure driving membrane between the ultrafiltration membrane and the reverse osmosis membrane, and the unique aperture size and surface charge performance enable the nanofiltration membrane to effectively separate high-valence salt ions and organic matters with molecular weight of more than 200Da, so the nanofiltration membrane has wide application prospect in the fields of water softening, seawater desalination, dye removal, food processing, wastewater treatment and the like. However, nanofiltration products in the market generally have poor salt separation performance and low flux, and the main modification methods of the nanofiltration membrane at present comprise adding an auxiliary agent or nanoparticles into a water phase to increase the hydrophilicity of a membrane surface and the effective area of the membrane, or adding an aprotic solvent with the solubility close to that of polyamide into an oil phase to increase the porosity of a separation layer, but the addition of the additives improves the flux of the nanofiltration membrane to a certain extent, but seriously reduces the salt rejection performance of the nanofiltration membrane.
Aquaporins are ideal water molecule channels with extremely strong water permeability and single permselectivity, allowing only water molecules to pass through at high speed. At present, the aquaporin composite membrane is mainly a phospholipid bilayer membrane containing aquaporin adsorbed on the surface of a basement membrane, wherein the phospholipid containing aquaporin is combined with the basement membrane only by hydrophilic acting force, the strength of the composite membrane is extremely low, and the aquaporin is easy to be inactivated by pollution and external influence.
Disclosure of Invention
The invention mainly aims to provide a composite nanofiltration membrane containing aquaporin and a preparation method thereof, so as to solve the problem of low strength of the aquaporin composite membrane in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a composite nanofiltration membrane containing aquaporin, the method comprising: step S1, arranging the aquaporin vesicles and a polyamine aqueous phase monomer solution on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the polyamine aqueous phase monomer solution comprises polyamine, a surfactant, an acid acceptor and water; step S2, carrying out secondary surface treatment on the surface treatment porous supporting layer by using a polybasic acyl chloride oil phase monomer solution to obtain a composite nanofiltration preparation membrane; and step S3, drying the composite nanofiltration preparation membrane to obtain a composite nanofiltration membrane, wherein the composite nanofiltration membrane comprises a porous support layer and a polyamide layer formed by polymerization, and aquaporin vesicles are dispersed in the polyamide layer.
Further, the step S1 includes: step S11, dispersing the aquaporin vesicles in polyamine aqueous phase monomer solution to form first dispersion liquid; and step S12, carrying out first surface treatment on the porous supporting layer by using the first dispersion liquid to obtain the surface-treated porous supporting layer.
Further, the aquaporin in the aquaporin vesicle is one or more of aquaporin Z, aquaporin 1, aquaporin S, aquaporin TIP, aquaporin PIP, aquaporin Y and aquaporin NIP.
Further, the porous support layer is a polysulfone membrane, a polyethersulfone membrane, a sulfonated polyetheretherketone membrane, a polyamide-polyimide membrane, a polyvinylidene fluoride membrane or a polyvinylpyrrolidone membrane, and preferably, the thickness of the porous support layer is 30 to 60 μm and the thickness of the polyamide layer is 100 to 200 nm.
Further, the composite nanofiltration membrane is a flat membrane, a hollow fiber membrane or a spiral membrane.
Further, in the polyamine aqueous phase monomer solution, the mass content of the polyamine is 2-6%, and the mass content of the surfactant is 0.01-0.5%; preferably, the pH value of the polyamine aqueous phase monomer solution is more than 7, and preferably 10-12.5.
Further, the polyamine is selected from one or more of aliphatic polyamine, alicyclic polyamine and aromatic amine polyamine with 2-4 amino functional groups, preferably the polyamine is selected from one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, amicrol, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, piperazine, 1, 3-dipiperidinopropane, 4-aminomethylpiperazine, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, ethanolamine, diethanolamine, hexamethylenediamine and diglycolamine; preferably, the surfactant is selected from any one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, N-methyl pyrrolidone, sodium laurate, sodium stearate, glyceryl stearate, sorbitan, fatty acid glyceride, span, dodecyl betaine and quaternary ammonium compound; preferably, the acid acceptor is selected from one or more of triethylamine, sodium hydroxide, sodium bicarbonate and trisodium phosphate.
Further, in the above polyamine aqueous phase monomer solution, the mass content of the aquaporin vesicles is 1 to 30%, and preferably, step S11 includes: mixing polyamine, a surfactant, an acid acceptor and water to form a first mixed system; stirring the first mixed system at a speed of 400-600 r/min for 10-30 min to obtain a polyamine aqueous phase monomer solution; mixing the aquaporin vesicles with the polyamine aqueous-phase monomer solution to form a second mixed system; and stirring the second mixed system for 30-120 min at a speed of 50-150 r/min to obtain a first dispersion liquid.
Further, the step S12 includes: immersing the porous support layer into the first dispersion liquid, and keeping for 15-300 s; and removing water on the surface of the impregnated porous support layer to obtain the surface-treated porous support layer.
Further, the mass content of the acid chloride-based compound in the polybasic acid chloride oil phase monomer solution is 0.05 to 5%, preferably the acid chloride-based compound is selected from one or more of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyldicarbonyl chloride, trimesoyl chloride, succinyl chloride, butanetriacyl chloride, glutaryl chloride, pentanedioyl chloride, adipoyl chloride, hexanetriyl chloride, cyclopropane triacyl chloride, cyclobutane triacyl chloride, cyclopentane tetracoyl chloride, cyclohexane triacyl chloride, cyclohexane tetracoyl chloride and tetrahydrofuran diacyl chloride, and the solvent of the polybasic acid chloride oil phase monomer solution is selected from n-hexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, ISOparE、ISOparGOne or more of benzene, toluene and xylene.
Further, the step S2 includes: and (3) immersing the surface treatment porous support layer into a polybasic acyl chloride oil phase monomer solution, and keeping for 10-200 s to obtain the composite nanofiltration preparation membrane.
Further, the step S3 includes: carrying out heat treatment on the composite nanofiltration preparation membrane at the temperature of 60-120 ℃ for 3-10 min to obtain a pre-drying membrane; soaking the pre-dried film in deionized water at the temperature of 60-80 ℃ for 60-300 s to obtain a wet film; soaking the wet membrane in 6-15% of humectant for 1-10 min, and then carrying out heat treatment at 60-120 ℃ for 3-10 min to obtain the composite nanofiltration membrane.
Further, the step S3 includes: dipping the composite nanofiltration preparation membrane in a polyamine water-phase monomer solution for 10-200 s to obtain a secondary dipping composite nanofiltration preparation membrane; carrying out heat treatment on the secondary immersion composite nanofiltration preparation membrane for 3-10 min at the temperature of 60-120 ℃ to obtain a pre-drying membrane; soaking the pre-dried film in deionized water at the temperature of 60-80 ℃ for 60-300 s to obtain a wet film; soaking the wet membrane in 6-15% of humectant for 1-10 min, and then carrying out heat treatment at 60-120 ℃ for 3-10 min to obtain the composite nanofiltration membrane.
According to another aspect of the invention, a composite nanofiltration membrane containing aquaporin is provided, and the composite nanofiltration membrane is prepared by any one of the preparation methods.
By applying the technical scheme of the invention, the aquaporin exists in the composite nanofiltration membrane in the mode of aquaporin vesicles, and the aquaporin vesicles cannot be polluted by the outside, so that high activity can be maintained; step S1, loading aquaporin vesicles and polyamine, a surfactant and an acid acceptor in the first dispersion liquid on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the surfactant is added to facilitate the spreading of a polyamine water phase and the aquaporin vesicles on the porous support layer to promote the sufficient reaction of subsequent amine and acyl chloride, and the acid acceptor can neutralize acid formed by the subsequent interfacial polymerization reaction to promote the proceeding of equilibrium reaction; in the step S2, in the process of performing the second surface treatment on the surface treatment porous supporting layer by using the polyacyl chloride oil phase monomer solution, in-situ polymerization reaction is performed on polyamine and polyacyl chloride to generate a polyamide preparation layer, so that a composite nanofiltration preparation membrane compounded by the polyamide preparation layer and the porous supporting layer is obtained, and in the in-situ polymerization reaction process, the water channel protein vesicles are wrapped in the polyamide preparation layer, so that the binding force of the water channel protein in the composite nanofiltration membrane is high, and the strength of the composite nanofiltration membrane is ensured; then, through the drying treatment of the step S4, the polyamide preparation layer is converted into a polyamide layer, and the aquaporin vesicles are dispersed in the polyamide layer; the strong water permeability and single selective permeability of the aquaporin are fully exerted, the water flux of the membrane is obviously improved on the premise of keeping the excellent salt rejection performance of the composite nanofiltration membrane, the hydrophilicity of the surface of the membrane is improved, and the anti-pollution capacity of the membrane is enhanced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a scanning electron micrograph of a composite nanofiltration membrane according to example 1 of the present invention; and
figure 2 shows a scanning electron micrograph of the composite nanofiltration membrane according to comparative example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art of the present application, in the phospholipid bilayer membrane containing aquaporin adsorbed on the surface of the base membrane in the prior art, the binding force between the phospholipid of aquaporin and the base membrane is low, which results in low strength of the composite membrane, and the protein is easy to be polluted and inactivated. The preparation method comprises the following steps: step S1, arranging the aquaporin vesicles and a polyamine aqueous phase monomer solution on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the polyamine aqueous phase monomer solution comprises polyamine, a surfactant, an acid acceptor and water; step S2, carrying out secondary surface treatment on the surface treatment porous supporting layer by using a polybasic acyl chloride oil phase monomer solution to obtain a composite nanofiltration preparation membrane; and step S3, drying the composite nanofiltration preparation membrane to obtain a composite nanofiltration membrane, wherein the composite nanofiltration membrane comprises a porous support layer and a polyamide layer formed by polymerization, and aquaporin vesicles are dispersed in the polyamide layer.
The aquaporin exists in the composite nanofiltration membrane in the mode of aquaporin vesicles, and is not polluted by the outside, so that high activity can be maintained; step S1, loading aquaporin vesicles and polyamine, a surfactant and an acid acceptor in the first dispersion liquid on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the surfactant is added to facilitate the spreading of a polyamine water phase and the aquaporin vesicles on the porous support layer to promote the sufficient reaction of subsequent amine and acyl chloride, and the acid acceptor can neutralize acid formed by the subsequent interfacial polymerization reaction to promote the proceeding of equilibrium reaction; in the step S2, in the process of performing the second surface treatment on the surface treatment porous supporting layer by using the polyacyl chloride oil phase monomer solution, in-situ polymerization reaction is performed on polyamine and polyacyl chloride to generate a polyamide preparation layer, so that a composite nanofiltration preparation membrane compounded by the polyamide preparation layer and the porous supporting layer is obtained, and in the in-situ polymerization reaction process, the water channel protein vesicles are wrapped in the polyamide preparation layer, so that the binding force of the water channel protein in the composite nanofiltration membrane is high, and the strength of the composite nanofiltration membrane is ensured; then, through the drying treatment of the step S4, the polyamide preparation layer is converted into a polyamide layer, and the aquaporin vesicles are dispersed in the polyamide layer; the strong water permeability and single selective permeability of the aquaporin are fully exerted, the water flux of the membrane is obviously improved on the premise of keeping the excellent salt rejection performance of the composite nanofiltration membrane, the hydrophilicity of the surface of the membrane is improved, and the anti-pollution capacity of the membrane is enhanced.
The step S1 may be performed by first impregnating the porous support layer to load the polyamine, the surfactant and the acid acceptor in the polyamine aqueous phase monomer onto the surface of the porous support layer, and then coating the aquaporin vesicles onto the surface of the porous support layer to obtain the surface-treated porous support layer. However, in this method, since a large number of aquaporin vesicles are required due to the loss during coating, it is preferable that the step S1 includes: step S11, dispersing the aquaporin vesicles in polyamine aqueous phase monomer solution to form first dispersion liquid; and step S12, carrying out first surface treatment on the porous supporting layer by using the first dispersion liquid to obtain the surface-treated porous supporting layer. Through the mode of firstly dispersing the aquaporin vesicles in the polyamine aqueous phase monomer solution and then carrying out surface treatment, the aquaporin vesicles can enter the surface of the porous supporting layer along with the monomers in the polyamine aqueous phase monomer solution, so that the loss caused by coating is avoided, and the aquaporin vesicles can be uniformly distributed on the surface of the porous supporting layer.
The aquaporin used in the aquaporin vesicle of the present application may be aquaporin commonly used in the prior art, and in order to control cost and achieve a desired water flux and salt rejection rate, the aquaporin in the aquaporin vesicle is preferably one or more of aquaporin Z, aquaporin 1, aquaporin S, aquaporin TIP, aquaporin PIP, aquaporin Y and aquaporin NIP.
The porous support layer used in the present application may be a porous membrane commonly used in a nanofiltration membrane in the prior art, and preferably, the porous support layer is a polysulfone membrane, a polyethersulfone membrane, a sulfonated polyetheretherketone membrane, a polyamide-polyimide membrane, a polyvinylidene fluoride membrane, or a polyvinylpyrrolidone membrane, and preferably, the porous support layer has a thickness of 30 to 60 μm and the polyamide layer has a thickness of 100 to 200 nm.
In a preferred embodiment of the present application, the composite nanofiltration membrane is preferably a flat membrane, a hollow fiber membrane or a spiral membrane.
In order to improve the in-situ polymerization efficiency, the polyamine aqueous phase monomer solution is preferably selected, the mass content of the polyamine is 2-4%, the phenomenon that the polyamide layer is too thick and the membrane flux is reduced due to overhigh amine content is avoided, and the phenomenon that the water flux and the desalination are low due to overlow amine content is also avoided; the mass content of the surfactant is 0.01-2%; preferably, the pH value of the polyamine aqueous phase monomer solution is more than 7, and preferably 10-12.5. By controlling the pH value range, acid produced in the interfacial polymerization reaction can be neutralized as soon as possible, the in-situ polymerization reaction is promoted, and a more compact functional layer is prepared.
The polyamine of the present application may be selected from polyamines commonly used in polyamide synthesis, for example, the polyamine is selected from one or more of aliphatic polyamines, alicyclic polyamines and aromatic amine polyamines having 2 to 4 amino functional groups, and preferably the polyamine is selected from one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, amiphenol, ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, diethylene triamine, piperazine, 1, 3-dipiperidyl propane, 4-aminomethylpiperazine, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, ethanolamine, diethanolamine, hexanediol amine and diglycolamine. Wherein, the membrane prepared by piperazine, pentanediamine and hexanediol amine monomer has outstanding water flux and desalting effect.
The surfactant used in the present application may be referred to the prior art, and preferably the above surfactant is selected from any one or more of sodium dodecylbenzene sulfonate, sodium lauryl sulfate, N-methylpyrrolidone, sodium laurate, sodium stearate, glyceryl stearate, sorbitan, glyceryl fatty acid ester, span, dodecyl betaine and quaternary ammonium compound. The sodium dodecyl benzene sulfonate, the sodium stearate, the glyceryl stearate and the like have more outstanding performances.
As described above, the acid acceptor of the present application mainly functions to adjust the pH to be greater than 7, and thus, there are many kinds of acid acceptors that can be used in the present application, and in order to more efficiently adjust the amine solution to an appropriate pH, it is preferable that the acid acceptor is selected from one or more of triethylamine, sodium hydroxide, sodium bicarbonate, and trisodium phosphate.
In the test process, the inventor of the present application finds that although the water flux and the salt rejection rate of the present application increase with the increase of the usage amount of the aquaporin vesicles, when the usage amount of the aquaporin vesicles increases to a certain degree, the water flux and the salt rejection rate cannot be increased without limitation, or even can be reduced, which may cause that the performance of polyamide formed by in-situ polymerization is affected by the excessive usage amount of the aquaporin vesicles, so in order to balance the manufacturing cost and the filtering effect, the present application preferably selects that the mass content of the aquaporin vesicles is 1 to 30% in the polyamine aqueous phase monomer solution.
In order to disperse the aquaporin vesicles as uniformly as possible in the polyamine aqueous monomer solution, it is preferable that the above step S11 includes: mixing polyamine, a surfactant, an acid acceptor and water to form a first mixed system; stirring the first mixed system at a speed of 400-600 r/min for 10-30 min to obtain a polyamine aqueous phase monomer solution; mixing the aquaporin vesicles with the polyamine aqueous-phase monomer solution to form a second mixed system; and stirring the second mixed system for 30-120 min at a speed of 50-150 r/min to obtain a first dispersion liquid. Firstly, stirring a first mixed system formed by polyamine, a surfactant, an acid receiving agent and water at a high speed to uniformly disperse the substances in a short time; and then the aquaporin vesicles are dispersed in the polyamine aqueous phase monomer solution through low-speed stirring, so that the uniform dispersion effect is ensured, and the damage of stirring to the aquaporin vesicles is avoided. Further, during the test, the inventors of the present application found that step S12 includes: immersing the porous support layer into the first dispersion liquid, and keeping for 15-300 s; and removing water on the surface of the impregnated porous support layer to obtain the surface-treated porous support layer. Through the operation, as much first dispersion liquid as possible is fixed on the surface of the porous support layer, so that the thickness of a polyamide layer formed by subsequent in-situ polymerization is ensured.
The polybasic acid chloride used in the present invention may be selected from conventional techniques, and preferably, in order to match the polyamine, the mass content of the acid chloride-based compound in the oil-phase monomer solution of the polybasic acid chloride is preferably 0.05 to 5%, and preferably, the acid chloride is preferably acid chloride-basedThe compound is selected from one or more of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyldicarbonyl chloride, trimesoyl chloride, succinyl chloride, butanetriacyl chloride, glutaryl chloride, pentanedioyl chloride, adipoyl chloride, hexanetriyl chloride, cyclopropanetriacyl chloride, cyclobutanetriacyl chloride, cyclopentane tetracoyl chloride, cyclohexane triacyl chloride, cyclohexane tetracoyl chloride and tetrahydrofuran diacid chloride. Meanwhile, in order to improve the solubility of the polybasic acid chloride, the solvent of the oil-phase monomer solution of the polybasic acid chloride is preferably selected from n-hexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, ISOparE、ISOparGOne or more of benzene, toluene and xylene.
In another preferred embodiment of the present application, the step S2 includes: and (3) immersing the surface treatment porous support layer into a polybasic acyl chloride oil phase monomer solution, and keeping for 10-200 s to obtain the composite nanofiltration preparation membrane. The step S2 allows the in-situ polymerization reaction to proceed sufficiently, and thus the polyamide pre-layer with more reliable strength is obtained.
In order to prepare a dry film excellent in water flux and desalting performance, it is preferable that the above step S3 includes: carrying out heat treatment on the composite nanofiltration preparation membrane at the temperature of 60-120 ℃ for 3-10 min to obtain a pre-drying membrane; soaking the pre-dried film in deionized water at the temperature of 60-80 ℃ for 60-300 s, and taking out to obtain a wet film; soaking the wet membrane in 6-15% of humectant for 1-10 min, and then carrying out heat treatment at 60-120 ℃ for 3-10 min to obtain the composite nanofiltration membrane. The first heat treatment promotes the reaction of the monomers in the composite nanofiltration pre-membrane, and then the pre-dried membrane is washed, and a second heat treatment can be performed to obtain a dried composite nanofiltration membrane. The humectant can be one commonly used in the prior art for forming a nanofiltration membrane wet film, such as glycerin and the like.
In addition, in order to further improve the encapsulation effect on the aquaporin vesicles, it is preferable that the step S3 includes: dipping the composite nanofiltration preparation membrane in a polyamine water-phase monomer solution for 10-200 s to obtain a secondary dipping composite nanofiltration preparation membrane; carrying out heat treatment on the secondary immersion composite nanofiltration preparation membrane for 3-10 min at the temperature of 60-120 ℃ to obtain a pre-drying membrane; soaking the pre-dried film in deionized water at the temperature of 60-80 ℃ for 60-300 s to obtain a wet film; and soaking the wet membrane in 6-15% of humectant for 1-10 min, and then carrying out heat treatment at 60-120 ℃ for 3-10 min to obtain the composite nanofiltration membrane. The composite nanofiltration preparation membrane is soaked in polyamine aqueous phase monomer solution before drying, so that polyamine monomer is formed on the surface of the formed polyamide preparation layer, and the polyamine monomer can be further polymerized with the unreacted oil phase monomer on the outer surface of the polyamide preparation layer in the subsequent drying process, so that the thickness of the formed polyamide layer is increased, and the better wrapping effect on the aquaporin vesicles is realized.
In another exemplary embodiment of the present application, there is provided a composite nanofiltration membrane containing aquaporin, which is prepared by any one of the above-mentioned preparation methods. The aquaporin exists in the composite nanofiltration membrane in the mode of aquaporin vesicles, and is not polluted by the outside, so that high activity can be maintained; the extremely strong water permeability and single selective permeability of the aquaporin are fully exerted, the water flux of the membrane is obviously improved on the premise of keeping the excellent salt rejection performance of the composite nanofiltration membrane, the hydrophilicity of the surface of the membrane is improved, and the anti-pollution capacity of the membrane is enhanced.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
(1) Mixing 48g of piperazine, 1.6g of sodium dodecyl benzene sulfonate, 32g of triethylamine (used as an acid acceptor) and 1470.2g of deionized water, adding 0.2g of NaOH into the mixed solution to adjust the pH value of the solution to 10 to form a first mixed system, stirring the first mixed system at a high speed of 500r/min for 0.5h until the mixed solution is completely dissolved to obtain a polyamine aqueous phase monomer solution, adding 48g of a 3mg/ml aquaporin Z solution (aquaporin vesicle solution) into the polyamine aqueous phase monomer solution to form a second mixed system, and stirring the second mixed system at a low speed of 100r/min for 2h to obtain a first dispersion liquid; mixing trimesoyl chloride 1g and ISOparE999g of solvent is mixed and stirred at a high speed of 500r/min until the benzene is benzene-IIIThe formyl chloride is completely dissolved to form a polybasic acyl chloride oil phase monomer solution.
(2) Immersing the polysulfone support membrane into the first dispersion liquid for 30s, then taking out the polysulfone support membrane, and removing redundant aqueous solution on the surface and the back of the support membrane by using nitrogen or wiping cloth until no obvious water drops exist, thereby obtaining the surface-treated porous support layer.
(3) And (3) immersing the surface treatment porous support layer into a polyacyl chloride oil phase monomer solution, reacting for 30s, taking out, and removing the redundant oil phase solution on the surface, so that a polyamide preparation layer containing water channel protein is generated on the surface of the surface treatment porous support membrane, and the composite nanofiltration preparation membrane is formed.
(4) And (2) carrying out heat treatment on the composite nanofiltration preparation membrane in an oven at 80 ℃ for 5min to obtain a pre-drying membrane, soaking the pre-drying membrane in deionized water at 60 ℃ for 5min, washing the pre-drying membrane with 10% of glycerol to obtain a washing membrane, and drying the washing membrane at 80 ℃ for 5min to obtain the composite nanofiltration membrane containing the water channel protein.
Example 2
Mixing 48g of piperazine, 1.6g of sodium dodecyl benzene sulfonate, 32g of triethylamine and 1502.2g of deionized water, adding 0.2g of NaOH to adjust the pH value of the solution to about 10 to form a first mixed system, stirring the first mixed system at a high speed of 500r/min for 0.5h until the solution is completely dissolved to obtain a polyamine aqueous phase monomer solution, adding 16g of 3mg/ml of AQPZ solution (aquaporin vesicle solution) into the polyamine aqueous phase monomer solution to form a second mixed system, and stirring the second mixed system at a low speed of 100r/min for 2h to obtain a first dispersion liquid; mixing trimesoyl chloride 1g and ISOparE999g of solvent is mixed and stirred at a high speed of 500r/min until the trimesoyl chloride is completely dissolved to form the polybasic acyl chloride oil phase monomer solution.
Otherwise, the same procedure as in example 1 was repeated.
Example 3
48g of piperazine, 1.6g of sodium dodecyl benzene sulfonate, 32g of triethylamine and 1486.2g of deionized water are mixed, 0.2g of NaOH is added into the mixture to adjust the pH value of the solution to about 10, a first mixed system is formed, and the first mixed system is stirred at a high speed of 500r/minStirring for 0.5h until the polyamine aqueous phase monomer solution is completely dissolved to obtain a polyamine aqueous phase monomer solution, adding 32g of 3mg/ml AQPZ solution (aquaporin vesicle solution) into the polyamine aqueous phase monomer solution to form a second mixed system, and stirring the second mixed system at a low speed of 100r/min for 2h to obtain a first dispersion liquid; mixing trimesoyl chloride 1g and ISOparE999g of solvent is mixed and stirred at a high speed of 500r/min until the trimesoyl chloride is completely dissolved to form the polybasic acyl chloride oil phase monomer solution.
Otherwise, the same procedure as in example 1 was repeated.
Example 4
Mixing 48g of piperazine, 1.6g of sodium dodecyl benzene sulfonate, 32g of triethylamine and 1438.2g of deionized water, adding 0.2g of NaOH to adjust the pH value of the solution to about 10 to form a first mixed system, stirring the first mixed system at a high speed of 500r/min for 0.5h until the solution is completely dissolved to obtain a polyamine aqueous phase monomer solution, adding 80g of 3mg/ml of AQPZ solution (aquaporin vesicle solution) into the polyamine aqueous phase monomer solution to form a second mixed system, and stirring the second mixed system at a low speed of 100r/min for 2h to obtain a first dispersion liquid; mixing trimesoyl chloride 1g and ISOparE999g of solvent is mixed and stirred at a high speed of 500r/min until the trimesoyl chloride is completely dissolved to form the polybasic acyl chloride oil phase monomer solution.
Otherwise, the same procedure as in example 1 was repeated.
Example 5
Mixing 48g of piperazine, 1.6g of sodium dodecyl benzene sulfonate, 32g of triethylamine and 1358.2g of deionized water, adding 0.2g of NaOH to adjust the pH value of the solution to about 10 to form a first mixed system, stirring the first mixed system at a high speed of 500r/min for 0.5h until the solution is completely dissolved to obtain a polyamine aqueous phase monomer solution, adding 160g of 3mg/ml of AQPZ solution (aquaporin vesicle solution) into the polyamine aqueous phase monomer solution to form a second mixed system, and stirring the second mixed system at a low speed of 100r/min for 2h to obtain a first dispersion liquid; mixing trimesoyl chloride 1g and ISOparE999g of solvent is mixed and stirred at a high speed of 500r/min until the trimesoyl chloride is completely dissolved to form a polybasic acyl chloride oil phase monomerAnd (3) solution.
Otherwise, the same procedure as in example 1 was repeated.
Example 6
The difference from example 1 is that the mass content of aquaporin vesicles in the first dispersion is 20%.
Example 7
The difference from example 1 is that the mass content of aquaporin vesicles in the first dispersion is 30%.
Example 8
The difference from example 1 is that the mass content of aquaporin vesicles in the first dispersion was 35%.
Comparative example 1
Mixing 48g of piperazine, 1.6g of sodium dodecyl benzene sulfonate, 32g of triethylamine and 1518.2g of deionized water, adding 0.2g of NaOH to adjust the pH value of the solution to 10 to form a first mixed system, and stirring the first mixed system at a high speed of 500r/min for 0.5h until the first mixed system is completely dissolved to obtain a polyamine aqueous phase monomer solution; mixing trimesoyl chloride 1g and ISOparE999g of solvent is mixed and stirred at a high speed of 500r/min until the trimesoyl chloride is completely dissolved to form the polybasic acyl chloride oil phase monomer solution.
Otherwise, the same procedure as in example 1 was repeated.
The composite nanofiltration membranes prepared in the above examples and comparative examples are respectively at 2000mg/l MgSO4And 500mg/l NaCl solution, 75psi test pressure and 25 ℃ solution temperature, in a cross-flow membrane test bench test evaluation, the test results are shown in Table 1.
TABLE 1
Examples 9 to 11
Examples 9, 10, 11 and example 1 differ from each other in that the piperazine concentration was 1%, 2% and 6%, and the detection method was the same as above, and the detection results are shown in Table 2.
TABLE 2
Examples 12 to 14
Examples 12, 13, 14 and example 1 differ from each other in that piperazine was replaced with 1,3, 5-triaminobenzene, pentanediamine, and hexanediol amine, respectively, as described above, and the results are shown in Table 3.
TABLE 3
Examples 15 to 17
Examples 15, 16, 17 and example 1 differ from each other in that the sodium dodecylbenzenesulfonate content in the aqueous monomer solution of the polyamine was 0.05%, 0.5% and 1%, respectively, and the test methods were the same as those described above, and the test results are shown in Table 4.
TABLE 4
Examples 18 to 20
Examples 18, 19 and 20 differ from example 1 in that the membranes were prepared by adding an acid acceptor to the polyamine to adjust the pH of the aqueous solution to 5, 8 and 11, and the test results are shown in table 5, as described above.
TABLE 5
Examples 21 to 24
The difference from example 1 is that the stirring time and speed of the first mixing system and the stirring speed and time of the second mixing system in step (1) are different, and are shown in table 6.
TABLE 6
The composite nanofiltration membranes of examples 21 to 24 were subjected to the same detection method as above, and the detection results are shown in table 7.
TABLE 7
Examples 25 to 30
Examples 25, 26, 27, 28, 29, and 30 are different from example 1 in that the polysulfone support membrane was immersed in the aqueous phase for 15s, 60s, 120s, 180s, 300s, and 350s for different periods of time, and the detection method was the same as above, and the detection results are shown in Table 8.
TABLE 8
Examples 31 to 36
Examples 31, 32, 33, 34, 35, and 36 differ from example 1 in the baking temperature, and the effect of different baking temperatures of 60 ℃, 70 ℃, 90 ℃, 100 ℃, 120 ℃, and 150 ℃ on the activity of vesicle-encapsulated protein was examined. The other steps are the same as example 1, the detection method is the same as above, and the detection results are shown in Table 9.
TABLE 9
Example 37
The aqueous solution was prepared as in comparative example 1 by first soaking the polysulfone based membrane in 1600g of aquaporin solution for 30s, taking out the membrane and draining it in air, then putting the membrane in the aqueous solution of comparative example 1, and the rest of the procedure was the same as in example 1.
Example 38
The polysulfone based membrane treated with the aqueous phase of comparative example 1 was drained and soaked in 1600g of aquaporin solution for 30s, and the other steps were the same as in example 1.
The test methods are the same as above, and the test results are shown in Table 10.
Experimental results show that in the preparation of the composite nanofiltration membrane added with the aquaporin, the aquaporin content, the dipping time in the water phase and the post-treatment drying temperature have important influences on the separation performance of the nanofiltration membrane. The content of aquaporins and the dipping time in a water phase are related to the adsorption quantity of proteins on a basal membrane, the improvement of membrane flux and the salt interception performance are directly influenced, and the aquaporins encapsulated by vesicles cannot influence the protein activity at the drying temperature of over 100 ℃, so that the use of a nanofiltration membrane at higher temperature cannot be limited by adding the aquaporins.
According to the comparison between the example 1 and the comparative example 1, the flux of the nanofiltration membrane is not greatly improved by pre-coating a layer of the aquaporin before the support membrane enters the water phase, which is probably related to the larger pore size of the support membrane, and a large amount of vesicles encapsulating the aquaporin are lost from the support membrane along with water, while the flux of the nanofiltration membrane is improved more closely by adding the water phase directly in the example 1 or coating a layer of the aquaporin after the water phase in the example 38.
In addition, the composite nanofiltration membrane of example 1 and comparative example 1 is detected by a scanning electron microscope, the detection results are respectively shown in fig. 1 and fig. 2, it can be seen from fig. 1 that a large number of aquaporin vesicles are embedded in the piperazine polyamide layer, and no such vesicles appear in fig. 2.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the aquaporins exist in the composite nanofiltration membrane in the mode of aquaporin vesicles, and cannot be polluted by the outside, so that high activity can be maintained; step S1, loading aquaporin vesicles and polyamine, a surfactant and an acid acceptor in the first dispersion liquid on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the surfactant is added to facilitate the spreading of a polyamine water phase and the aquaporin vesicles on the porous support layer to promote the sufficient reaction of subsequent amine and acyl chloride, and the acid acceptor can neutralize acid formed by the subsequent interfacial polymerization reaction to promote the proceeding of equilibrium reaction; in the step S2, in the process of performing the second surface treatment on the surface treatment porous supporting layer by using the polyacyl chloride oil phase monomer solution, in-situ polymerization reaction is performed on polyamine and polyacyl chloride to generate a polyamide preparation layer, so that a composite nanofiltration preparation membrane compounded by the polyamide preparation layer and the porous supporting layer is obtained, and in the in-situ polymerization reaction process, the water channel protein vesicles are wrapped in the polyamide preparation layer, so that the binding force of the water channel protein in the composite nanofiltration membrane is high, and the strength of the composite nanofiltration membrane is ensured; then, through the drying treatment of the step S4, the polyamide preparation layer is converted into a polyamide layer, and the aquaporin vesicles are dispersed in the polyamide layer; the strong water permeability and single selective permeability of the aquaporin are fully exerted, the water flux of the membrane is obviously improved on the premise of keeping the excellent salt rejection performance of the composite nanofiltration membrane, the hydrophilicity of the surface of the membrane is improved, and the anti-pollution capacity of the membrane is enhanced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. The preparation method of the composite nanofiltration membrane containing the aquaporin is characterized by comprising the following steps:
step S1, arranging the aquaporin vesicles and a polyamine aqueous phase monomer solution on the surface of the porous support layer to obtain a surface-treated porous support layer, wherein the polyamine aqueous phase monomer solution comprises polyamine, a surfactant, an acid acceptor and water;
step S2, carrying out secondary surface treatment on the surface treatment porous supporting layer by using a polybasic acyl chloride oil phase monomer solution to obtain a composite nanofiltration preparation membrane; and
step S3, drying the composite nanofiltration preparation membrane to obtain the composite nanofiltration membrane, wherein the composite nanofiltration membrane comprises a porous support layer and a polyamide layer formed by polymerization, aquaporin vesicles are dispersed in the polyamide layer,
the step S1 includes:
step S11, dispersing the aquaporin vesicles in polyamine aqueous phase monomer solution to form first dispersion liquid;
step S12, carrying out first surface treatment on the porous supporting layer by using the first dispersion liquid to obtain a surface-treated porous supporting layer,
in the polyamine aqueous phase monomer solution, the mass content of the aquaporin vesicles is 1-30%, and the step S12 includes:
immersing the porous supporting layer into the first dispersion liquid, and keeping for 15-180 s;
and removing the water on the surface of the impregnated porous support layer to obtain the surface-treated porous support layer.
2. The method for producing according to claim 1, wherein the aquaporin in the aquaporin vesicle is one or more of aquaporin Z, aquaporin 1, aquaporin S, aquaporin TIP, aquaporin PIP, aquaporin Y, and aquaporin NIP.
3. The preparation method according to claim 1, wherein the porous support layer is a polysulfone membrane, a polyethersulfone membrane, a sulfonated polyetheretherketone membrane, a polyamide-polyimide membrane, a polyvinylidene fluoride membrane, or a polyvinylpyrrolidone membrane.
4. The method according to claim 3, wherein the thickness of the porous support layer is 30 to 60 μm, and the thickness of the polyamide layer is 100 to 200 nm.
5. The preparation method of claim 1, wherein the composite nanofiltration membrane is a flat membrane, a hollow fiber membrane or a spiral membrane.
6. The method according to claim 1, wherein the polyamine aqueous phase monomer solution contains 2 to 6% by mass of the polyamine and 0.01 to 0.5% by mass of the surfactant.
7. The method of claim 6, wherein the polyamine aqueous monomer solution has a pH greater than 7.
8. The method according to claim 7, wherein the pH of the polyamine aqueous monomer solution is 10 to 12.5.
9. The method according to claim 5, wherein the polyamine is one or more selected from the group consisting of aliphatic polyamines, alicyclic polyamines and aromatic amine polyamines having 2 to 4 amino functional groups.
10. The method according to claim 9, wherein the polyamine is selected from the group consisting of one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, amicrol, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, piperazine, 1, 3-dipiperidinopropane, 4-aminomethylpiperazine, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, ethanolamine, diethanolamine, hexamethylenediamine, and diglycolamine.
11. The method according to claim 9, wherein the surfactant is selected from any one or more of sodium dodecylbenzene sulfonate, sodium lauryl sulfate, N-methylpyrrolidone, sodium laurate, sodium stearate, glyceryl stearate, sorbitan, glyceryl fatty acid esters, span, dodecyl betaine, and quaternary ammonium compounds.
12. The method of claim 9, wherein the acid acceptor is selected from one or more of triethylamine, sodium hydroxide, sodium bicarbonate, and trisodium phosphate.
13. The method for preparing a composite material according to claim 1, wherein the step S11 includes:
mixing polyamine, a surfactant, an acid acceptor and water to form a first mixed system;
stirring the first mixed system at a speed of 400-600 r/min for 10-30 min to obtain the polyamine aqueous phase monomer solution;
mixing the aquaporin vesicles with the polyamine aqueous-phase monomer solution to form a second mixed system; and
and stirring the second mixed system at a speed of 50-150 r/min for 30-120 min to obtain the first dispersion liquid.
14. The method according to claim 1, wherein the mass content of the acid chloride-based compound in the oil-phase monomer solution of the polyacyl chloride is 0.05 to 5%.
15. The method according to claim 14, wherein the acid chloride-based compound is selected from the group consisting of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyldicarbonyl chloride, trimesoyl chloride, succinyl chloride, butanetriacyl chloride, glutaryl chloride, pentanedioyl chloride, adipyl chloride, hexanetriyl chloride, cyclopropanetriacyl chloride, cyclobutanetriacyl chloride, cyclopentanetetrayl chloride, cyclohexanetriyl chloride, cyclohexanetetrayl chloride, and tetrahydrofuran diacid chloride, and the solvent of the monomer solution of the oil phase of the polybasic acid chloride is selected from the group consisting of n-hexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, ISOparE、ISOparGOne or more of benzene, toluene and xylene.
16. The method for preparing a composite material according to claim 1, wherein the step S2 includes:
and immersing the surface treatment porous support layer into the polyacyl chloride oil phase monomer solution, and keeping for 10-200 s to obtain the composite nanofiltration preparation membrane.
17. The method for preparing a composite material according to claim 1, wherein the step S3 includes:
carrying out heat treatment on the composite nanofiltration preparation membrane at the temperature of 60-120 ℃ for 3-10 min to obtain a pre-drying membrane;
soaking the pre-dried film in deionized water at the temperature of 60-80 ℃ for 60-300 s to obtain a wet film;
and soaking the wet membrane in 6-15% of humectant for 1-10 min, and then carrying out heat treatment at 60-120 ℃ for 3-10 min to obtain the composite nanofiltration membrane.
18. The method for preparing a composite material according to claim 1, wherein the step S3 includes:
dipping the composite nanofiltration preparation membrane in the polyamine aqueous phase monomer solution for 10-200 s to obtain a secondary dipping composite nanofiltration preparation membrane;
carrying out heat treatment on the secondary immersion composite nanofiltration preparation membrane for 3-10 min at the temperature of 60-120 ℃ to obtain a pre-drying membrane;
soaking the pre-dried film in deionized water at the temperature of 60-80 ℃ for 60-300 s to obtain a wet film;
and soaking the wet membrane in 6-15% of humectant for 1-10 min, and then carrying out heat treatment at 60-120 ℃ for 3-10 min to obtain the composite nanofiltration membrane.
19. A composite nanofiltration membrane containing aquaporin, wherein the composite nanofiltration membrane is prepared by the preparation method of any one of claims 1 to 18.
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